Aminodiarylsulphonpyrazolone azodyestuffs



Patented Sept. 18, 1928.

UNITED STATES PATENT OFFICE.

HUGO SCHWEITZER, OF WIESDORF, NEAR COLOGNE, AND WILHELM NEELIVTEIER, OF 'LEVERKUSEN, NEAR COLOGNE, GERMANY, ASSIGNORS TO GRASSELLI DYESTUFF CORPORATION, OF NEW YORK, N. Y., A CORPORATION OF DELAWARE AMINODIARYLSULIPHONPYRAZOLONE 'AZODYESTUFFS.

No Drawing. Application filed January 5, 1926, Serial No: 79,476, and. in .Germany January 8, 1925.

This invention relates to new azodyestuffs prepared from the pyrazolones of aininodiarysulphones and their derivatives, such as sulphonic acid, carboxylic acids, hydroxycarboxylic acids, etc. Such pyrazolones have not been used heretofore for the preparation of azodyestufi's.

We have found that the azodyestufi's obtainable from them have far superior fastness properties than thosemade from known pyrazolones.

They give yellow shades on wool which with respect to the properties of fastness to fulling, perspiration, and level dyeing, as well as unusual fastness to light, are not obtainable with pyrazolone dyestuffs heretofore known. The same is true of their use as lake dyestuffs. In the latter case, one obtains yellow, water soluble dyestuffs which are fast to lime and water when made up as distemper paints and which show an extraordinary fastness to light. These pyrazolones Yare also suitable as coupling components in the formation of chrome mordant dyestufis or wool, especially those which contain anb-hydroxycarboxylic acid residue. With these products, one obtains'wool dyestuffs which give very fast greenish yellows and also red tints that are fast to potting.

Example 1. 173 parts by weight of o-sulphanilic acid are diazotized in theusual way and coupled in the presence of sodium acetate with 408 The pyrazolone is obtained by reduction of the condensation product of i-toluol-l-sulphinic acid and 2-nitr0-l-chlor benzoll-sulphonic acid conversion of thejamine so obtained into the hydrazine by the well known methods and conversion, of the latter into the pyrazolone by means of acetoacetic ester. The pyrazolone is produced according to the following graphical formulae:

r NH:

HQCOSOFOSOHEI HNO:

' N=N- on soul orncocrn-ooocnn which dissolves easily It is a colorless powder difliculty in aqueous in alkali and with more sou: mo canton I If p-sulphanilic acid is used in place of o-sulphanilic acid, a somewhat redder dyestulf is obtained possessing similar characteristics.

Example 2.

.107 parts by weight of o-toluidine are diazotized and coupled in the presence of sodium acetate with 408 parts by weight of the methylpyrazoline obtained from 4' methyl-2-aminodiphenylsulphonet-sulphonic acid. The dyestutf is worked up in the usual way.' Its characteristics are about those of the product of Example 1. 'It probably has the formula:

Example 3.

327 parts by Weight of y-methyl-2-animodiphenylsulphonel-sulphonic acid are diazotized and coupled in the presence of sodium acetate .with 430 parts by weight of pyra'zolone carboxylic acid obtained from 1-methyl- 2 aminodiphenylsulphone- L-sulphonic acid. The dyestu'lf is salted out, isolated and dried. In distemper paints it dyes a greenish yellow.

It probably has the formula:

I CH3 The color is fast to lime and water and very H tainable by reduction of the condensation product of 41-toluol-1-sulphinic acid and 2- nitro-l-phlorbenzol, is used in place of the 4:-

inethyl-Q-aminodiphenylsulphone-t-sulphonacid, a dyestufl' of similar characteristics produced.

niethylphrazolone obtained from 1"- methyl-2 aminodiphzgnylsulphone is a colorless crystalline powder melting at 17 8180. Example 4. 171.5 parts by weight of 4-chlor-2-nitraniline are diazotized and'coupled in the absence of sodium acetate with 408 parts by weight of the pyrazolone of Example 1. The dyestufl is worked up in the usual manner. 'In

distemper paints it dyes a reddish yellow,

fast to lime and very fast to light. It probably has the formula:

. soa1 11 S02 01 NO: 0 Example 5.

327 parts by weight of 4-methyl-2-aminodiphenyisulphonel-sulphonic acid are diazotized and coupled in the presence of sopyrazolone carboxylic acid obtained from 4- 00- dium acetate with 430 parts by Weight of the methyl 4 aminodiphe nylsulphone 2 sul- .phonic acid. The dyestuif is salted out and Worked up in the usual manner. It probably has the formula:

soar

HOaS

Indistemper paints it dyes a greenish yellow. Its characteristics of fastness are about those of the product of Example 3.

The pyrazolone carboxylic acid is obtained by reduction of the condensation product of l-toluol-l-sulphinic acid and t-nitro-l-chlorbenzol-Q-sulphonic acid, conversion ofthe amine so obtained by the Well known methods into the hydrazine and conversion of the latter into the yrazolone carboxylic acid by means of oxa acetic ester. It 'is a colorless powder which dissolves easily in alkali and aqueous sodium acetate solution and which yields dyestuffs by combining with diazocompounds. 4

I Example 6. 173 parts by Weight of o-sulphanilic acid are diazotized and coupled in the presence of sodium acetate With 474 parts by weight of the pyrazolone obtained from 2-amino-4'- hydroxydiphenylsulphone 4 3-sulphocarboxylic acid. The dyestuff is worked up in the well known manner. It dyes wool a greenish yellow which when afterohromed becomes very fast without any real change of shade. It probably has the formula:

The '2-amino4'-hydroxydiphenylsulphone- 4.3-sulphocar boxylic acid is obtained by reduction of the condensation product of salicylsulphinicacid 'and 2-nitro-1-chlorbenzol- 4-sulphonic acid.- The mthylpyrazolone from. the 2-amino-4-hydroxydiphenylsulphone-4-3-sulphocarboxylic acid is a color-- less powder which dissolves easily in alkali and aqueous sodium acetate solution. It

combines with diazocompounds to form mordant dyestufi'sp If the o-sulphanilic acid of this example is replaced by p-sulphan'ilic acid.

or by o-toluidine, products of similar characteristics are obtained.

not. As is apparent from the description the benzene nuclei may contain as substituents,

, an aromatic diazo compound witha'pyrazolone of. a sulphonated aminodiarylsulphone.-

4. As a new product the azo dyestufi con-.

sisting of the product obtainable-by coupling a sulphona-ted aromatic diazo compound with a pyrazolone of a sulphonated aminodiarylsulphone. i j

5. As a new product theazodyestuif having in the free state most probably the general formula Example 7.

143.5 parts by weight of 4-chlor-2-amino- I phenol are diazotized and coupled, in a sodium hydroxide solution with the pyrazolone of Example 6. The dyestufi is worked u'pin the usual way and dyes wool orange shades which when afterchromed are changed to a fast red. The color is fast to potting. The dyestufi probably has the formula:

The products made according to this invention are yellow to orange powders which when dissolved in sulphuric acid gives solutions of the same colors as. their dyeings; In the claims the term pyrazolone of an aminodiarylsulphone is intended to include the compounds of the general formula:

X C =N arm? which is'a yellow powder, soluble in .water, soluble in concentrated sul huric with a yellow color, and dyeing woo from an acid bath greenish-yellow shades of excellent fastness to light, fulling 'and perspiration.

6.. As new products, the azodyestufis which are obtainable by coupling an aromatic diazo comppund with a methyl pyrazolone of a sulphonated amino-diarylsulphone.

7. As new products, the azodyestufl's which are obtainable by coupling a sulphonated aro-' matic diazo compound with a-pyrazolone of an amino-diarylsulphone.

8. As new'products, the azodyestufi's which are obtainable by coupling a sulphonated aro-v matic diazo compound with a methyl pyrazow lone of an amino-diarylsulphone. r

9. As new products, the azodyestufls which are obtainable by-coupling a sulphonated aromatic diazo compound with a methyl pyrazolone of a sulphonatcd amino-diarylsulphone.

10. As new products, the azodyestufl's having in the free state the formula:

wherein X stands for hydrogen, an alkyl group or a carboxylic acid group and wherein the benzene nuclei may be substituted or X--C=N so 7 in which R stands for an aromatic group, X

stands for hydrogen, an alkyl group or a carbozylic acid group, in which the sor' substituent is in either the 2- or 4-p0siti'0n to the nitrogen, andin which the benzenen'uclei attached to the sulphone group may be further substituted. 4

11. As new products, the azodyestuffs having in the free state the formula:

in whichR stands for an aromatic group in which the S'O:O'substituent is in either the 2-- or 4-position t6 the nitrogen, and in which the benzene nuclei attached to the I sulphone group may be further substituted.

12. As new products, the azodyes tufishaving in the free state the formula:

' in which R stands for anaro'matic group and HUGO SCHWEITZER-v WILHELM NEELMEIER. 

